CN1119636A - Inhibition of the polymerization of vinylaromatic or vinyliphatic compounds - Google Patents

Inhibition of the polymerization of vinylaromatic or vinyliphatic compounds Download PDF

Info

Publication number
CN1119636A
CN1119636A CN95115274.2A CN95115274A CN1119636A CN 1119636 A CN1119636 A CN 1119636A CN 95115274 A CN95115274 A CN 95115274A CN 1119636 A CN1119636 A CN 1119636A
Authority
CN
China
Prior art keywords
nitrosophenol
oxide compound
tetramethyl piperidine
inhibitor
methyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN95115274.2A
Other languages
Chinese (zh)
Inventor
T·凯尔
M·考夫霍尔德
B·赫尔帕普
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Huels AG
Original Assignee
Huels AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=25939374&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=CN1119636(A) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Priority claimed from DE19515450A external-priority patent/DE19515450A1/en
Application filed by Huels AG filed Critical Huels AG
Publication of CN1119636A publication Critical patent/CN1119636A/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K15/00—Anti-oxidant compositions; Compositions inhibiting chemical change
    • C09K15/04—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds
    • C09K15/30—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds containing heterocyclic ring with at least one nitrogen atom as ring member
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B63/00—Purification; Separation; Stabilisation; Use of additives
    • C07B63/04—Use of additives
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/48—Separation; Purification; Stabilisation; Use of additives
    • C07C67/62—Use of additives, e.g. for stabilisation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/20—Use of additives, e.g. for stabilisation

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Analytical Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Water Supply & Treatment (AREA)
  • Materials Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Polymerisation Methods In General (AREA)
  • Hydrogenated Pyridines (AREA)

Abstract

The present invention provides a method for inhibiting the polymerisation of vinyl-aromatic or vinyl-aliphatic cpds. at elevated temp, in the absence of air comprises adding, as inhibitor, 4-hydroxy- or 4-acetylamino-2,2,6,6-tetramethyl-piperidin-N-oxyl or a mixt. thereof with p-nitrosophenol or 2-methyl-4-nitroso-phenol.

Description

Ethene suppressing base aromatics or alicyclic vinyl compounds of group polymeric method
The present invention relates to a kind of particularly method of styrene polymerization of aromatic vinyl or alicyclic vinyl compounds of group of when distillation, avoiding.
Vinylbenzene is the raw material of preparation polystyrene and multipolymer.Owing to transform during vinylbenzene not exclusively and generate by product in preparation, thereby must carry out fractionation by distillation.Because vinylbenzene is easy to take place thermopolymerization under distillation temperature, so must add a kind of inhibitor to this technology.These inhibitor for example nitrophenyl phenolic, nitrosobenzene phenols, to tert.-butyl pyrocatechol or sulphur, be known and be used to big technical scale.By document US-PS 4967027 and EP-B-0229515 also as can be known, also can use the array configuration of various inhibitor.
In view of its thermo-sensitivity, big industrially under vacuum, distill vinylbenzene without any exception.Known most of inhibitor must be just effective in the presence of oxygen.Consequent basic problem is that enough oxygen is provided in the tower that moves under vacuum.
Therefore, need provide new is suitable for as used high temperature under the distillation condition and the aromatic vinyl of shortcoming or the polymerization retarder of alicyclic vinyl compounds of group as described in not having.
Now find unexpectedly, when high temperature, inhibitors 4-hydroxyl-2,2,6,6-tetramethyl piperidine-N-oxide compound (oxy1) (HTMPO) and 4-acetylaminohydroxyphenylarsonic acid 2,2,6,6-tetramethyl piperidine-N-oxide compound (AA-TEMPO) separately or with right-nitrosophenol or 2-methyl-4-nitrosophenol combination, even under oxygen free condition also the polymerization to ethene suppressing base aromatics or alicyclic vinyl compounds of group have good inhibitor performance.
2804 No. 449 patent specifications of DE have been pointed out the validity of nitroso compound when vacuum distilling vi-ny l aromatic monomers compound prevailingly.2 of there protection, 6-dinitrobenzene-p-Cresol is the same with other common nitrocresol class to have these compounds only is the shortcoming of retarding agent.Retarding agent can slow down the formation of polymkeric substance, but can not prevent fully, so always form small amount of polymer.Opposite with retarding agent, inhibitor is looked its validity and different, prevents the formation of polymkeric substance in the regular hour fully, but after this loses efficacy at once.
Known HTMPO and AA-TEMPO are free radical aceeptors in the styrene polymerization that free radical causes.But exceed is when vacuum distilling vinylbenzene, fabulous restraining effect to be arranged unexpectedly.In addition, beat all also have, 2-methyl-4-nitrosophenol/HTMPO, p-Nitrosophenol/HTMPO, 2-methyl-4-nitroso-group-phenol/AA-TEMPO and p-Nitrosophenol/AA-TEMPO combination has not only also shown inhibiting synergy in the presence of oxygen but also under oxygen free condition, that is to say that the effect of mixture is than independent making good use of with HTMPO or AA-TEMPO.P-Nitrosophenol/HTMPO or p-Nitrosophenol/AA-TEMPO combination has shown strong especially synergy.Wherein the effect of 50% mixture is fabulous.
Method of the present invention can adopt styrenic (for example alpha-methyl styrene), esters of acrylic acid, methyl acrylic ester and the Vinylstyrene of vinylbenzene, replacement.
Inhibitor of the present invention or inhibitor mixed thing of the present invention are at 90 to 140 ℃, and preferred 100 to 120 ℃ of temperature are issued to maximum effectiveness.The add-on of inhibitor can change with distillation condition.Usually, stable degree is directly proportional with the inhibitor quantity of adding.
Proved conclusively already, be as the criterion in aromatic vinyl or alicyclic vinyl compounds of group, HTMPO or AA-TEMPO separately or with p-Nitrosophenol or 2-methyl-combined consumption of 4-nitrosophenol be 50 to 200ppm, the preferred result that can offer the best 100 to 150ppm the time.
This depends on the temperature of distillating mixture and required inhibition degree especially.
If HTMPO or AA-TEMPO are used in combination with p-Nitrosophenol or 2-methyl-4-nitrosophenol, then its ratio of mixture is 90: 10 to 10: 90, preferred 50: 50.
The preparation of inhibitor of the present invention can be known by document (for example DE-OS 42 19 459 and Annalen are 417, the 120 pages).
AA-TEMPO??????????????????????????HTMPO
4-acetylaminohydroxyphenylarsonic acid 2.2.6.6.-4-hydroxyl-2.2.6.6.-
Tetramethyl piperidine-tetramethyl piperidine-
N-oxide compound N-oxide compound
Fusing point=143 ℃ fusing point=64-67 ℃
White-orange color yellow-orange
Embodiment
By measuring the validity that polymkeric substance is determined inhibitor or inhibitor mixed thing with gravimetry by following rules:
In the three-necked flask of a 500ml, put into new distillatory vinylbenzene of 300ml and inhibitor to be tested, under agitation condition, be heated to 110 ℃ and writing time.Sampling is determined polymer content by carry out gravimetric analysis with methanol extraction at interval.Obtain " polymkeric substance-time " curve, wherein selective polymer content reaches 3% o'clock time measuring as inhibitor or inhibitor mixed thing validity.Test (constantly is blown into nitrogen bubble) and carries out under nitrogen atmosphere.The results are shown in table 1.
Table 1
Under nitrogen atmosphere, when using various inhibitor, vinylbenzene reaches for 3% the used residence time of polymer content at 110 ℃.
Inhibitor The residence time when forming 3% polymkeric substance
The vinylbenzene of Yi Zhiing not 48 minutes
HTMPO?????????????50ppm 107 minutes
HTMPO?????????????100ppm 128 minutes
P-Nitrosophenol 50ppm 122 minutes
Inhibitor The residence time when forming 3% polymkeric substance
P-Nitrosophenol 100ppm 176 minutes
2-methyl isophthalic acid-nitrosophenol 50ppm 169 minutes
HTMPO/ 50ppm p-Nitrosophenol 50ppm 184 minutes
HTMPO/ 50ppm 2-methyl-4-nitrosophenol 50ppm 197 minutes
HTMPO/ 75ppm 2-methyl isophthalic acid-nitrosophenol 25ppm 174 minutes
AA-TEMPO??????????????????????50ppm 102 minutes
AA-TEMPO?????????????????????100ppm 123 minutes
AA-TEMPO/ 50ppm 2-methyl-4-nitrosophenol 50ppm 184 minutes
AA-TEMPO/ 75ppm 2-methyl-4-nitrosophenol 25ppm 162 minutes
AA-TEMPO/ 50ppm p-nitrosophenol 50ppm 169 minutes
In addition, compare with the nitrosobenzene phenols, HTMPO+AA-TEMPO also has the advantage that shelf stability is good and toxicity is little, and is difficult for occuring spontaneous decomposition.

Claims (6)

1. under high temperature and airfree condition, come ethene suppressing base aromatics or alicyclic vinyl compounds of group polymeric method by adding a kind of inhibitor or inhibitor mixed thing, it is characterized in that, with 4-hydroxyl-2,2,6,6-tetramethyl piperidine-N-oxide compound or 4-acetylaminohydroxyphenylarsonic acid 2,2,6,6-tetramethyl piperidine-N-oxide compound mixes separately or with p-Nitrosophenol or 2-methyl-4-nitrosophenol makes inhibitor.
2. by the described method of claim 1, it is characterized in that 4-hydroxyl-2,2,6,6-tetramethyl piperidine-N-oxide compound or 4-acetylaminohydroxyphenylarsonic acid 2,2,6, the ratio of 6-tetramethyl piperidine-N-oxide compound and p-Nitrosophenol or 2-methyl-4-nitrosophenol is 90: 10 to 10: 90.
3. by the described method of claim 1, it is characterized in that, 4-hydroxyl-2,2,6,6-tetramethyl piperidine-N-oxide compound or 4-acetylaminohydroxyphenylarsonic acid 2,2,6, the ratio of 6-tetramethyl piperidine-N-oxide compound and p-Nitrosophenol or 2-methyl-4-nitrosophenol is 50: 50.
4. by the described method of claim 1 to 3, it is characterized in that, be as the criterion in aromatic vinyl or alicyclic vinyl compounds of group, 4-hydroxyl-2,2,6,6-tetramethyl piperidine-N-oxide compound or by 4-hydroxyl-2,2,6, the consumption of the mixture that 6-tetramethyl piperidine-N-oxide compound and p-Nitrosophenol or 2-methyl-4-nitrosophenol are formed is 50 to 200ppm.
5. by the described method of claim 1 to 3, it is characterized in that, be as the criterion in aromatic vinyl or alicyclic vinyl compounds of group, 4-acetylaminohydroxyphenylarsonic acid 2,2,6,6-tetramethyl piperidine-N-oxide compound or by 4-acetylaminohydroxyphenylarsonic acid 2,2,6, the consumption of the mixture that 6-tetramethyl piperidine-N-oxide compound and p-Nitrosophenol or 2-methyl-4-nitrosophenol are formed is 50 to 200ppm.
6. by the described method of claim 1 to 5, it is characterized in that inhibitor or inhibitor mixed thing are effective under 90 to 140 ℃ of temperature.
CN95115274.2A 1994-08-19 1995-08-15 Inhibition of the polymerization of vinylaromatic or vinyliphatic compounds Pending CN1119636A (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DEP4429485.9 1994-08-19
DE4429485 1994-08-19
DE19515450A DE19515450A1 (en) 1994-08-19 1995-04-27 Inhibition of the polymerization of vinyl aromatic or vinyl aliphatic compounds
DE19515450.9 1995-04-27

Publications (1)

Publication Number Publication Date
CN1119636A true CN1119636A (en) 1996-04-03

Family

ID=25939374

Family Applications (1)

Application Number Title Priority Date Filing Date
CN95115274.2A Pending CN1119636A (en) 1994-08-19 1995-08-15 Inhibition of the polymerization of vinylaromatic or vinyliphatic compounds

Country Status (6)

Country Link
EP (1) EP0697386B1 (en)
JP (1) JPH0859524A (en)
CN (1) CN1119636A (en)
CZ (1) CZ211495A3 (en)
ES (1) ES2126185T3 (en)
PL (1) PL310071A1 (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102295513A (en) * 2010-06-25 2011-12-28 中国石油化工股份有限公司 Method for refining isoprene by extractive rectification
CN102295499A (en) * 2010-06-25 2011-12-28 中国石油化工股份有限公司 Polymerization inhibitor for inhibiting polymerization of vinyl compound
CN110382556A (en) * 2017-03-09 2019-10-25 埃科莱布美国股份有限公司 Polymerization inhibitor composition

Families Citing this family (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19510184A1 (en) * 1995-03-21 1996-09-26 Basf Ag 4-acylaminopiperidine-N-oxyls
GB9614854D0 (en) * 1996-07-15 1996-09-04 Marks A H & Co Ltd Free radical scavengers
US6409887B1 (en) 1996-07-15 2002-06-25 Aah Marks And Company Limited Polymerization inhibitor
ID20069A (en) * 1997-03-20 1998-09-24 Ciba Sc Holding Ag POLYMERIZATION INHIBITOR PROCESS
FR2761680B1 (en) * 1997-04-07 1999-05-28 Rhodia Chimie Sa COMPOSITION INHIBITING RADICAL POLYMERIZATION OF ETHYLENICALLY UNSATURATED MONOMERS AND METHOD FOR INHIBITING RADICAL POLYMERIZATION OF SAID MONOMERS
US5932735A (en) * 1997-06-13 1999-08-03 Ciba Specialty Chemicals Corporation Derivatives of 1-oxyl-4-hydroxy-2,2,6,6-tetramethylpiperidine as polymerization inhibitors for (meth)acrylate monomers
DE19725519A1 (en) * 1997-06-17 1998-12-24 Basf Ag Mixture of substances containing compounds containing vinyl groups and stabilizers
US5869717A (en) * 1997-09-17 1999-02-09 Uop Llc Process for inhibiting the polymerization of vinyl aromatics
US5955643A (en) * 1997-10-17 1999-09-21 Nalco/Exxon Energy Chemicals, L.P. Composition and method for inhibiting polymerization during the anaerobic of styrene
KR20010106405A (en) 1998-07-14 2001-11-29 시바 스폐셜티 케미칼스 홀딩 인코포레이티드 Derivatives of 1-Oxyl-4-Hydroxy- Or 4-Amino-2,2,6,6-Tetramethylpiperidine As Polymerization Inhibitors For (Meth)Acrylate Monomers
JP2000169429A (en) * 1998-12-10 2000-06-20 Mitsubishi Rayon Co Ltd Production of high-purity (meth)acrylic ester
US6395942B1 (en) 1999-08-10 2002-05-28 Uop Llc Increasing the thermal stability of a vinyl aromatic polymerization inhibitor
US6395943B1 (en) 1999-08-10 2002-05-28 Uop Llc Process for inhibiting the polymerization of vinyl aromatic compounds
US6300533B1 (en) * 1999-08-16 2001-10-09 Uniroyal Chemical Company, Inc. Inhibition of polymerization of ethylenically unsaturated monomers
JP5675184B2 (en) * 2010-06-18 2015-02-25 伯東株式会社 Polymerization inhibitor composition for vinyl compound and method for preventing polymerization of vinyl compound using the same
WO2020205994A1 (en) 2019-04-02 2020-10-08 Ecolab Usa Inc. Pure chlorine dioxide generation system with reduced acid usage

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4105506A (en) 1977-02-24 1978-08-08 Cosden Technology, Inc. Polymerization inhibitor for vinyl aromatic compounds
US4654451A (en) 1985-12-27 1987-03-31 Atlantic Richfield Company Inhibiting polymerization of vinyl aromatic monomers
US4670131A (en) * 1986-01-13 1987-06-02 Exxon Chemical Patents Inc. Method for controlling fouling of hydrocarbon compositions containing olefinic compounds
US4967027A (en) 1987-12-22 1990-10-30 Mitsubishi Petrochemical Co., Ltd. Method of inhibiting polymerization of styrenes
DE4219459A1 (en) 1992-06-13 1993-12-16 Huels Chemische Werke Ag Process for the preparation of 2,2,6,6-tetramethylpiperidine-N-oxyl and its derivatives substituted in the 4-position
US5254760A (en) * 1992-07-29 1993-10-19 Ciba-Geigy Corporation Inhibiting polymerization of vinyl aromatic monomers
US5322960A (en) * 1993-04-15 1994-06-21 Nippon Shokubai Co., Ltd. Method for inhibiting polymerization of (meth) acrylic acid and esters thereof

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102295513A (en) * 2010-06-25 2011-12-28 中国石油化工股份有限公司 Method for refining isoprene by extractive rectification
CN102295499A (en) * 2010-06-25 2011-12-28 中国石油化工股份有限公司 Polymerization inhibitor for inhibiting polymerization of vinyl compound
CN110382556A (en) * 2017-03-09 2019-10-25 埃科莱布美国股份有限公司 Polymerization inhibitor composition
CN110382556B (en) * 2017-03-09 2021-10-15 埃科莱布美国股份有限公司 Polymerization inhibitor composition
RU2763926C2 (en) * 2017-03-09 2022-01-11 ЭКОЛАБ ЮЭсЭй ИНК. Polymerization inhibitor compositions

Also Published As

Publication number Publication date
CZ211495A3 (en) 1996-05-15
ES2126185T3 (en) 1999-03-16
EP0697386B1 (en) 1998-11-25
JPH0859524A (en) 1996-03-05
EP0697386A1 (en) 1996-02-21
PL310071A1 (en) 1996-03-04

Similar Documents

Publication Publication Date Title
CN1119636A (en) Inhibition of the polymerization of vinylaromatic or vinyliphatic compounds
US5888356A (en) Inhibition of polymerization of vinylaromatic or vinylaliphatic
CA1323634C (en) Methods and compositions for inhibiting styrene polymerization
EP0594341B1 (en) Compositions and methods for inhibiting vinyl aromatic monomer polymerization
CA1091616A (en) Polymerization inhibitor for vinyl aromatic compounds
KR100718064B1 (en) Method of inhibiting polymerization of aromatic vinyl
CA1267659A (en) Inhibiting polymerization of vinyl aromatic monomers
WO1998056746A1 (en) Polymerization inhibition of acrylates using blends of nitroxides
CA2099168A1 (en) Compositions and methods for inhibiting styrene polymerization
CA1288438C (en) Method and composition for inhibiting acrylate ester polymerization
JPH07502750A (en) Polymerization inhibiting composition of vinyl aromatic compound
EP0845448B1 (en) Inhibiting polymerization of vinyl aromatic monomers
US4654450A (en) Inhibiting polymerization of vinyl aromatic monomers
DE69401743T2 (en) Compositions and methods for inhibiting the polymerization of ethylenically unsaturated compounds
WO1998014416A1 (en) Compositions and methods for inhibiting vinyl aromatic monomer polymerization
ES2046168T3 (en) AQUEOUS POLYMER DISPERSIONS, A PROCEDURE FOR THEIR OBTAINING AND EMPLOYMENT.
JP3960508B2 (en) Method for inhibiting polymerization of styrenes
US4542231A (en) Stabilized ethylenically unsaturated organic compositions
NL7708218A (en) LIQUID COATING COMPOSITION WITH A HIGH SOLID CONTENT ON THE BASIS OF AN ACRYLIC COPOLYMER.
US5157175A (en) Composition and method for inhibition of styrene polymerization
US5285006A (en) Compressor fouling inhibition in vinyl acetate production units
US5648572A (en) Compositions and methods for inhibiting vinyl aromatic monomer polymerization
US4021476A (en) Vinyl acetate polymerization inhibitors
JPS63316745A (en) Prevention of polymerization of aromatic vinyl compound
US6863779B2 (en) Distillation of styrene

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
AD01 Patent right deemed abandoned
C20 Patent right or utility model deemed to be abandoned or is abandoned